Composition of matter



Patented Mar. 26, 1940 1 UNITED STATES COMPOSITION OF MATTER Melvin De Groote, University City, Mo, assignor,

by mesne assignments, to Petrolite Corporation, Ltd., a corporation of Delaware No Drawing. Application March 10, 1939, Serial No. 261,093

9 Claims.

This application is a continuation in part of my pending application for patent Serial No. 211,038, filed May 31, 1938, which has subsequently resulted in U. S. Patent No. 2,166,433, dated July 18, 1939.

My present invention consists of a new compound or composition of matter, consisting of a certain kind of complex amine derived by reaction between (a) acid esters obtained from phthalated monoricinolein, phthalated diricinolein, phthalated mono-olein, phthalated di-olein, phthalated mono-naphthenin, phthalated monoabietin, or similar materials.

One can obtain or manufacture chemical compounds whose composition is indicated by the following formulas:

H oruzc oocmm (011.120 oocmomn (OH.RCOO.C:H4)IN The compounds above described may be summarized by the following formula:

in which 1n represents the numeral 1, 2, or 3, 111. represents the numeral 0, 1, or 2, and m." represents the numeral 0, 1 or 2, with the proviso that m+m'+m"=3.

However, the radical C2H4 which appears in the above formula may represent any similar radical, such as a C3Hs radical, C4Hs radical, etc.,

. and therefore, the above formula may be re- In the above formulas, '1 represents a nonhydroxy aliphatic hydrocarbon radical, such as a methyl, ethyl, propyl, amyl, or similar radical; or T may represent a non-hydroxy alicyclic radical, such as a cyclohexyl radical, or a nonhydroxy aralkyl-radical, such as a benzyl radical; or the acylated radical obtained by replacing a hydrogen atom of the hydroxyl group of an alkylol radical by the acyl radical of a monobasic carboxy acid, such as acetic acid, butyric acid, oleic acid, stearic acid, naphthenic acid, abietic acid, or the like, all of which are characterized by having less than 32 carbon atoms. The alkylol radical prior to acylation may be a hydroxy alicyclic or a hydroxy aralkyl radical, provided that the hydroxy radical is attached to the aliphatic residue of the aralkyl radical. In the above formulas, OHRCOOH represents a hydroiwlated fatty acid, such as ricinoleic acid, hydroxystearic acid, dihydroxystearic acid, diricinoleic acid, triricinoleic acid, polyricinoleic acid, etc.; and OI-LRCOO represents the oxy acyl radical derived from such acid, i. e., the ordinary acid radical. Blown oils (oxidized oils) are not included.

As to the amines above described, which happen to be tertiary amines, it may be well to point out that these may be formed readily by a reaction involving an ester of the hydroxylated fatty acid and a corresponding amine. This may be illustrated in the following manner:

Reference is made to co-pending application for patent Serial No. 180,993, filed December 21, 1937, by Melvin De Groote, Bernhard Keiser and Charles M. Blair, Jr. If triethanolamine, as employed in the above formula, is replaced by ethyl diethanolamine, or by diethyl ethanolamine, then one would readily obtain the other two types of tertiary amines illustrated. Reference is made to co-pending application for patent Serial No. 206,904, filed May 9, 1938, by De Groote, Keiser and Blair, which subsequently resulted in U. S. Patent No. 2,167,349, dated July 25, 1939.

In the remaining three types of materials there is at least one amino hydrogen atom present. The manufacture of such type material may be illustrated by the following reactions:

on.n.ooon+0nc,mon OE.R.COO-CIE|OH OEBDOOSMCH-CsHn HI NH CsHu Similarreactionstotheoneimmediatelypreeedingraultinoompoimdssuchas:

OEROOOJHH: OILILCOOfisHc /NH 11 Conn CsHICHs DK-RCOO-CMHJ Naturally, if ethyl ethanolamine or a similar amine were to replace ethanolamine (monoethinolamine) one would obtain the remaining type at amine above illustrated.

Suitable primary and secondary amines which may be employed to produce materials of the kind above described include the following: diathanolamine, monoethanolamine, ethyl ethanolamine, methyl ethanolamine, propanolamine, dioropanolamine, propyl propanolamine, etc. other examples include cyclohexylamine, dicyclohexvlolamine, cyclohexyl ethanolamine, cyclohexyl propanolamine, benzyl ethanolamine, benzyl propanolamine, pentanolamine, hexanolamine, octyl ethanolamine, octadecylethanolamine, cyclohexmol ethanolamine, etc.

Similarly, suitable tertiary amines, which may be employed, include the following: triethanolamine, diethanolalkylamines, such as diethanol ethylamine, diethanol propylamine, etc. Other examples include diethanol methylamine, tripropanolamine, dipropauol methylamine, cyclohexmol diethanolamine, dicyclohexanol ethanolamine, cyclohexyl diethanolamine, dicyclohexyl ethanolamine, dicyclohexanol ethylamine, benzyl iiethanolamine, dibenzyl ethanolamine, benzyl :lipropanolamine, tripentanolarnine, trihexanolamine, ethyl hexyl ethanolamine, octadecyl di :thanolamine, polyethanolamine, etc.

aromas N-CsKNCsHaOE N-OsHuOGsHlOH N-CsHaOH CiHaO ClHAOH OIHIOH CimOH CsHaOGaHaOH CfllOCiHlOH HN HN clmo CaHlOH CSHIOE Such amines may serve as functional equivalents of the previously described amines and which are free from an ether linkage.

All the amines of the kind above described and characterized by the formula:

(OH.RC O 0.0:Ha) IN in which n represents a small whole numbe preferably less than 10, and m represents the numeral 1, 2 or 3, m represents the numeral 0, 1, or 2, and 111" represents the numeral 0, 1, or 2, with the proviso that m+m+m"=3, have four common characteristics. In the first place, these amines are not quaternary ammonium bases or salts thereof. The expression "quaternary ammonium is properly and conventionally applied to compounds in which all four hydrogen atoms of the ammonium radical NH4 have been replaced by a hydrocarbon radical or oxy-hydrocarbon radical, as, for example, in trimethyl phenyl ammonium hydroxide.

Secondly, an important characteristic which must be recognized is that these amine compounds are not amides. It is to be noted that an amide formation involves a product in which there is a direct linkage between the carboxylic carbon atom and the nitrogen atom in the amine. This is not the case in the compounds employed as intermediate raw materials for production of the compounds used as demulsifying agents in this process.

In the third place, it must be recognized that these compounds are derived only from basic amines. The word basic is employed to exclude amines having little or no basicity, such as the ordinary aromatic amines, or any amine having at least one aryl radical directly joined to the amino nitrogen atom. For this reason, these amine products which are herein contemplated as demulsifying agents and which necessarily are characterized by freedom from any aryl groups, as such, cannot be derived from aryl amines. They are derived solely from alkyl, alicyclic, or aralkyl amines having atleast one hydroxyl group present. It is true that in the aralkyl amines there is an aryl group present, but it is not directly attached to the nitrogen atom, as in the case of aryl amines, but in fact, represents nothing more or less than a substituted alkylamine. For instance, I consider benzylamine as being the primary amine, phenmethyl amine.

Finally, it must be recognized that these materials have not lost any basicity in the forms of the esteriiled amine and that they exhibit all the properties of a basic amine, that is, they combine with water to form a base presumably a substituted ammonium compound, but not quaternary ammonium compounds, insofar that there are always one, two or three unsubstituted hydrogen atoms of the ammonium radical present. They combine withvarious acids to form salts.

For example, they may be combined with acetic acid, hydrochloric acid, lactic acid, chloracetic acid, nitric acid, butyric acid, phosphoric acid, oxalic acid, or any suitable organic or inorganic acid. to form salts. It is understood that the reference in the specification and appended claims to the amines includes the basic form and the acid salts, as well as the amines themselves.

The new compositions of matter herein described have great demulsifying properties which are contributed, in part, by the amines, and it is immaterial whether the amine may be considered as being in any one of the following forms:

in which T represents the substituents for the amino hydrogen atoms of the parent ammonia from which all amines are hypothetically derived and X simply represents the acid radical of any acid employed. This statement applies with equal force and eil'ect to the final product, or composition of matter, which is also a basic amine of a more complex type.

Reference is again made to the formula which summarizes the various amines used as intermediate raw materials, viz:

in which the characters have their previous signiflance.

Attention is directed to the fact that where the substituted alkyl radical OH.R.COO.C2H appears, a suitable non-aryl radical other than an aliphatic residue may serve as the functional equivalent; for instance, an alicyclic radical derived from a cyclohexyl radical, or an aralkyi radical derived from a benzyl radical. In other words, in the hereto appended claims reference to the CYIH?" radical, as such, or as an alkyl radical or residue, is intended in the broad sense to include the alicyclic radicalor residues or the aralkyl radicals or residues which are the equivalent thereof. There is no intention to include an aromatic radical where there is a direct linkage between the aromatic nucleus and the amino hydrogen atom, for the reason that such products have little or no basicity and do not have the characteristic properties of the amines previously described.

In indicating the various hydroxylated tertiary amines of the non-aryl type which may be employed to produce the amine herein described, it is desirable to indicate that amines of the type where a hydroxy acyl radical replaces a hydrogen atom of the hydroxyl radical of the hydroxy tertiary amine, are not included within the broad class of hydroxy tertiary amines, unless there is another hydroxyl radical attached to the usual alkyl radical. For instance, if diethyl amino ethanol is treated with lactic acid so". as to form lactyl ethanol diethanolamine of the following formula:

on o

omcrLo-o-om.

C: sN

CIHI

then it is understood that such materials would not represent a hydroxy tertiary amine within the meaning or scope, as herein employed. If, on the other hand, triethanolamine were treated with lactic acid, so as to give monolactyl triethanolamine of the following composition:

then such compound would be included, due to the presence of one or more hydroxyl radicals attached to the alkyl radicals.

Similarily, in indicating the various hydroxylated primary or secondary amines of the nonaryl type which may be employed to produce the amine herein described, it is desirable to indicate that amines of the type where a hydroxyl acyl radical replaces a hydrogen atom of the hydroxyl radical of a hydroxy primary or secondary amine, are not included within the broad class of hydroxy tertiary amines, unless there is another hydroxyl'radical attached to the usual alkyl radical. For instance, if ethanolamine is treated with lactic acid, so as to form the lactyl derivative of the following formula:

then it is understood that such materials would not represent a hydroxy primary amine within the meaning or scope, as herein employed. The same would be true if the corresponding product derived from diethanolamine, provided that both hydroxy radicals has been esterified with lactic acid. If, on the other hand, diethanolamine were treated with lactic acid, so as to give monolactyl diethanolamine of the following composition:

on o

CH3CH.COCIH then such compound would be included, due to the presence of the hydroxyl radicals attached to the alkyl radicals.

The manufacture of compounds from tertiary amines is relatively simple, because no precautions are necessary to prevent amidification. The selected fatty oil and the selected hydroxy tertiary amine are mixed in suitable proportions and heated at some point above the boiling point of water, for instance, 110 C., and at point below the decomposition point of the amine or the fatty oil, for instance, 180 0., for a suitable period of time, such as two to eight hours. Mild agitation is employed. A catalyst, such as sodium oleate, sodium carbonate, caustic soda, etc., may be present in amounts of about one-half of 1%, or less. It is noted that the fatty acids are employed in this instance in the form of an ester, to wit, the glyceride, although as previously pointed out, other functional equivalents can be readily employed with equal facility. It is to be noted that the reactions above described do not take place to any appreciable extent if the fatty acid has been converted into the soap or salt. Such salts are not functional equivalents.

When, however, one is employing a hydroxy primary or a hydroxy secondary amine, precautions must be taken so that one gets a substantial percentage of products derived by esterification, rather than arnidification. Any suitable ester may be employed, but it is often most convenient to use the glyceride, for instance, triricinolein.

The selected glyceride and the selected hydroxy primary or secondary amine are mixed in suitable proportions and heated at some point above the boiling point of water, for instance, C., and below the decomposition point of the amine or fatty material, for instance, 180 C., for a suitable period of time, such as 4-24 hours. Mild agitation is employed. A catalyst, such as sodium oleate, sodium carbonate, caustic soda, etc., may be present in amounts of about or less. It is to be noted that the fatty acids are present in ester form and not in the form of the free acid, and thus there is no tendency to form the salt to any marked extent, and if conducted at the lower range of reaction temperatures, there is a decided tendency to form the esteriflcation products, rather than the amidification products.

In order to illustrate suitable examples of the amines which may be used as intermediate raw materials, the following examples are given:

Intermediate amineE:cample 1 Castor oil is employed. For sake of cofivenience, its molecular weight is considered as being 925. Commercial triethanolamine and castor oil in the proportion of one mole of castor oil to one mole of triethanolamine are heated to a temperature between and C. for about 2 hours. Mild agitation is employed. The reaction product so produced may be used as such, or may be converted into the acetate or other suitable form.

Intermediate amineExample 2 Polyethanolamine:

c mocimon N-o,H.oc,u.oH 0111.0 0,11,011'

is substituted for triethanolamine in Example 1.

Intermediate amine-E.'cample 3 Ethyl dihydroxy stearate is reacted in the previous manner with the various amines above enumerated in Examples 1 and 2. In this case three moles of ethyl dihydroxy stearate are reacted with one mole of the tertiary hydroxyamine.

Intermediate amineEa:ample 4 Methyl hydroxy stearate is employed to replace ethyl dihydroxy stearate in the examples indicated under Example 3 above.

Intermediate amineEa:ample 5 Castor oil (triricinolein) is employed. For convenience its molecular weight is considered as being 925. Commercial diethanolamine and castor oil in the proportion of two moles of castor oil to three moles of diethanolamine are heated at a temperature of 120-140 C. for about 12 hours. Mild agitation is employed. Loss of basicity is an indication of amidiflcation. Time of reaction may be extended or temperature lowered or raised so as to insure maximum esterification. The reaction product so produced may be used as such, or may be converted into the acetate or other suitable form.

Intermediate amine-Example 6 Ethanolamine is substituted for diethanolamine in Example 1, using three moles of ethanolamine for one mole of castor oil.

Intermediate amine-Example 7 Ethyl ethanolamine is substituted for diethanolamine in Example 1, using three moles of ethyl ethanolamine for one mole of castor oil.

Intermediate amine-Example 8 An ether amine of the following composition:

CzHcOCgUgOH is substituted for diethanolamine in Example 5.

Having prepared the relatively simpler intermediate amines of the kind previously described, the second step in the preparation of the new composition of matter is to produce acid esters of the kind obtainable by reaction between polybasic carboxy acids or their functional equivalents, such as the anhydrides and esters of detergent-forming acids or the like. Detergent-forming acids are monobasic carboxy acids, such as typical fatty acids, abietic acids, or naphthenic acids. Typical fatty acids are those which occur in naturally-occurring oils and fats and generally have 8 or more carbon atoms and not over 32 carbon atoms. Common examples include oleic acid, stearic acid, linoleic acid, linolenic acid, ricinoleic acid, erucic acid, palmitic acid, myristic acid, etc. These various acids combine with alkali -to produce soap or soap-like materials, and are commonly referred to as being monobasic detergent-forming acids. Blown oils (oxidized oils) are not included.

Detergent-forming acids combine with polyhydric alcohols to give esters characterized by the presence of at least one hydroxyl radical attached to the radical which replaces the carboxylic hydrogenation. Polyhydric alcohols include glycerol, ethylene glycol, propylene glycol, and other similar glycols, and also a polyhydroxy ether alcohol type of material such as diethylene glycol, diglycerol, triglycerol, etc. Such materials, whether produced from glycerol or from glycol or from two dissimilar polyhydric alcohols, are characterized by the fact that dehydration produces an oxygen linkage between two organic residues, and thus the material, in addition to having the properties of a polyhydric alcohol, has to some degree at least, the properties of an ether. As to the manufacture of esters from an alcohol, including polyhydric alcohols, and a carboxy acid, the usual procedure is esterification in presence of dry hydrochloric acid gas. Such method is satisfactory, provided that conditions are controlled so that complete esteriflcation does not take place, and thus result in a material containing no free hydroxyl in the polyhydric alcohol residue. For example, if diglycerol is esterified with four molecules of ricinoleic acid, the resultant product will not contain a free hydroxy group in the polyglycerol residue. However, if esteriflcation is continued so that one, two, or three ricinolcic acid residues are introduced, and so that three, two, or one free hydroxyi residues re- 7 ventional manner usually employed in such reac- I time.

It is, of course, obvious that esters may be produced as readily from naphthenic acid or abietic acid or the like, as from fatty acids. For sake of brevity. reference will be made particularly to fatty acids. A large number of materials derived from fatty acids and characterized by the presence of a free hydroxyl attached to the hydrocarbon radical which replaces the carboxylic hydrogen, is available in the open market and sold under the name of superglycerinated fats. Such materials are used as emulsifying agents, both in edible and non-edible products. They are derived from a wide variety of acids and a wide variety of polyhydric alcohols of both the ether type and the non-ether type. 1

The following formulas indicate the types derivable from non-hydroxylated monobasic carboxy acids: I

R.COO.Cs l

on (aco'ohoimon n.coo.cim.on accommommon on (acoohcimooim on on acooom OCIHI If derived from hydroxylated fatty acids, such 45 as hydroxystearlc acid, ricinoleic acid, and the like, the above formulas would correspond to the f llowing:

OH.R.COO.Ca I

(OH.R.COO)JC8HIOH OH.R.CO0.C$H|.OH 'on.a.coo.olmooimon -/0H (OH.R.COO)ICIHIOC8HI on on OH.-R.COO.Cs I

OCIHI If such products are reacted with polybasic carboxy acids, or their anhydrides, as, for example, phthalic acid or phthalic anhydride, one can obtain a large number of esters which are acidic esters in the sense that there is present a free carboxyl radical. In the following formulas, no attempt is made to show phthalic anhydride as the usual ortho compound, but it is shown as a .para compound, purely for the sake of convenience. The selection of phthalic acid is purely for purposes of illustration. Any one of a number of other acids may be employed.

ooc aooomm GOOH 00C COOH acoocanoodcoon 00C COOK 000 OOOH If, however, such materials were derived from hydroxylated fatty acids without involving the alcoholiform hydroxyl attached to the fatty acid radical, then the above formula would appear as follows:

oooOooon However, if one considers the reactions in which only the alcoholiiorm hydroxyl of the fatty acid radical, for example, ricinoleic acid, is involved in formation 01' the reaction products obtained, then they may be indicated by the following formulas:

coon

aooootn L ,inooo canon COOK aooootr'n oocOooon oocOooon oooC coon a.ooo

o.m.oocC ooon acoo coon

COOE

a.ooo.c,ntoocO-ooon In the examples shown above, where the ester is polybasic, one might remove the acidity of' one of the carboiwlic hydrogen atoms or two of the carbowlic hydrogen atoms in any feasible mannenthat is, by neutralization with an alkali or by conversion into an ester involving a re-' action with any suitable alcohol, 1. e., a monohydric, trihydrio, etc. In any event, however, the material derived by reaction between a polybasic acid or its functional equivalent and the hydroxylated ester type of Iatty material of the kind described, is always characterized by the presence of at least one free carboxyl radical.

Where reference is made to ricinoleic acid, by-

, droxysteslric acid, abietic acid, and the like, it is evident that certain simple derivatives, such as the halogenated compounds, are the obvious functional equivalents; for instance, chlorinated ricinoleic acid may be employed, instead of claims, reference to mono'sasic detergentorm ing carboxy acids includes such obvious inn"- tional edifivolents,

As o the manuiactizre of reagents from polycarbcxy acids and sdperglycerinated fate or the it need. s ply be stated. that these reagents have been pr d in the arts of plasticizers, do log agents, etc, that the method of producing the same is well known. Briefly stated, esterlfication takes place readily on the application of heat, and the reaction may be hastened by. employing a higher temperature, provided that decomposition does not take place;

or the reaction may be conducted in presence of an inert solvent, such as xylene, which may be removed after completion of reaction. The reaction can be hastened also by passing through the mixture 9. dried inert gas; or the reaction may be conducted under a reflux condenser, using material such as xylene and a water trap, so as to remove water as quickly as formed. Generally speaking, however, the reactions take place rapidly, quickly, and completely by simply heating the products together in stoichiometric proportions at a temperature somewhere above the boiling point of water, and particularly at'a temperature of about 110-160" 0., provided there is no decomposition. Phthalic anhydride is particularly suitable, because it does not decompose readily, whereas, some other acid, such as oxalic acid, may be equally desirable, but the temperature of esterification must be lower, of course, to prevent decomposition.

The polybasic acids which may be employed, including some having at least three carboxyl radicals, are phthalic, succinic, malic, iumaric, citric, maleic, adipic, tartaric, glutaric, diphenic,

naphthalic, oxalic, etc.

It is to be noted that the manufacture of the composition of matter in reality involves three diilerent esteriflcation reactions. For example, a fatty acid may be reacted with a tertiary 'hydroxyamine to give products of the kind indicated. Naturally, it the tertiary amine, such as triethanolamine, is reacted with a glyceride, the

reaction may, in essence, be a rearrangement reaction, rather than an esteriiication reaction,

although for purposes of classification, it may be considered as an esteriflcation reaction. The second esteriiication reaction involved is the one between the hydroxy fatty body of the kind described, such as superglycerinated fats and phthalic anhydride, or the like. Monoabietin or mononaphthenin, of course, may be considered broadly as a superglycerinated fat.

The-third esteriflcation reaction is between the two types of materials above described, the simpler amine always being characterized by the presence of an alcoholic-hydroxyl radical, and the ester being characterized by the presence of the carboxyl group. The last mentioned esteriiication reaction goes readily and is nothing more or less than a conventional esteriflcationreaction and requires no further elaboration.

' Composition of matter-Example 1 cal. This is a conventional esteriflcation reac tion, and the materials are intimately mixed and heated at approximately 120-160 C., with constant agitation, until samples taken from the batch and analyzed show substantially complete reaction. A suitable solvent may be present, and waterformed may be distilled 9i! continuously during the esterification process. The solvent may remain behind in the final product, or be removed, if desired.

Composition of matter-Example 2 Diphthalated mono-olein is substituted for diphthalated diricinolein in Composition of matter Example 1, immediately above.

Composition of matter-Example 3 Dimaleated monostearin is substituted for diphthalated diricinolein in Composition of matter Example 1 above.

Composition'of matter-Example 4 Dioxalated monoabletin is substituted for diphthalated dirlcinolein in Composition of matter Example 1 above.v

Composition of matter-Example 5 Dicitrated mononaphthenin is substituted for diphthalated diricinolein in Composition of matter Example 1 above.

Composition of matter-Example 6 An amine of the kind characterized by the product described under Intermediate amine Example 5 is substituted in the above Composition of matter Examples 1-5 for the intermediate amine therein employed.

It should be noted, however, that this particular product contains only two hydroxyl radicals available for esterification per atom of nitrogen. Insofar that some amidification may take place in following the directions in preparing the amine from diethanolamine in Intermediate amine Example 5 above, it is probably the safest procedure to determine the acetyl or hydroxyl value, before reacting in molecular proportions, so as to leave a free carboxyl radical.

Attention is directed to the fact that th alkylolamines are obtained in such a manner that they may be looked upon as being derivatives of dihydric-alcohols, for instance, the chlorhydrin of the dihydric alcohol, as indicated in the following manner:

i'lfiii i As previously stated, the C2H4 radical may be any one of a number of hydrocarbon radicals which are aliphatic, alicyclic or aralkyl in nature,

It is at once manifest that similar derivatives are available from glycerols, polyglycerols, and the like, as indicated by the following reaction:

It is not necessary to point out that the same types of reactions will produce secondary or teramine, monoglyceryl diethylamine, monoglycdipropylamine,

etc.,

diglyceryl propylamine which are functional eryl triglycerylamine,

equivalents of the various amines previously described for reaction with triricinolein and the like. When such amines are employed, instead of the radical CnH2n appearing in. a compound,. one would have in place thereof the radical -OH.CaHs-; or, in case the hydroxyl radical of those OH.C3H5- radical had been removed by esteriflcation with any available carboxyl, then the substituent which replaces the -C2H2n radical might be indicated by the formula D.CaH5-. All that has been said here in regard to functional equivalents will be per fectly obvious without further explanation to those skilled in the art. See U. S. Patent No. 2,091,704, dated August 31, 1937, to Duncan and McAllister; also U. S. Patent No. 2,042,621, dated June 2, 1936, toOlin.

Similarly, it is evident that where reference is made to phthalic acid, some simple derivative, such as chlorinated phthalic acid, brominated phthalic acid, methylated phthalic acid, or the like, would simply act as a functional equivalent. This applies not only to phthalic acid, but all the dibasic acids enumerated.

Similarly, it is evident that there is no intention to differentiate between isomeric forms. One isomeric form may serve as well as another. Attention is particularly called to the last two examples above, which are characterized especially by the presence of a free carboxyl radical other than the carboxyl radical derived from dibasic acid.

I desire to emphasize that any of the products obtained in the above examples, when employed as a demulsifier in the resolution of crude oil emulsions, may be used in the form of the amine by direct contact with an emulsion, without contact with water. It may be contacted with water, i. e., in the form of a solution, so as to produce in-a greater or lesser degree the amine base.

, be employed to give a suitable salt. As previously pointed out, any carboxylic hydrogen atom may be replaced by a suitable metallic atom, or an organic radical derived from an alcohol or from an amine. All such ionizable hydrogen atom equivalents are considered as the functional equivalent of the ionizable hydrogen atoms themselves, and such neutralized forms are included in the scope of the appended claims as the equivalent of the acidic form. It is realized that where a free carbowl and a basic amine residue exists in the same molecule, there may be a ten dency towards the formation of inner salts comparable to sulfanilic acid; but due to the size of the molecule involved, and perhaps for reasons of steric hindrance, I am not aware that such inner salts are formed.

Briefly, then, the preparation of the composition of matter herein contemplated depends on a reaction involving a polybaslc carboxy acid body, or its functional equivalent, as described,

and the complex amine of the kind described, in such a manner as to involve reactions other than salt formation. In other words, the complex amines are basic in nature, and therefore, could react with a; polybasic acid to forms. salt in a manner which, for sake of convenience, will be indicated by a somewhat simpler reaction, thus:

coon

ammoocxncoon or mNnloocmcooNa Such reactions are purely salt formationThe materials of the kind herein contemplated, regardless of their nature, are of the kind obtained by reactions other than salt formation, and also other than amidification.

I desire to emphasize that the expression "polybasic carboxy acid, as it appears in the claims, refers not only to the acid itself, but to any functional equivalent, such as the anhydride, the

acyl chloride, a salt form having at least two free carboxyls, such as mono-sodium citrate, etc. It is also understood that in the hereto appended claims the nature of the final product is not limited to the form having a free carboxylic hydrogen, but that such fre'e carboxylic hydrogen may actually be replaced by any functional equivalent of the kind previously described, for instance, a metallic atom, an ammonium radical, an amine radical, such as an amyiamine radical, benzylamine radical, ethanolamine radical, diethanolamine radical, triethanolamine radical, a hydrocarbon radical, such as an ethyl, methyl, propyl, or amyl radical, a radical derived from ethylene glycol, glycerol, or the like; a cyclohexyl radical, benzyl radical, etc. All such forms in which such ionizable hydrogen atom equivalent replaces an ionizable hydrogen atom, are obvious functional equivalents.

Attention is directed to the fact that the word amidiflcation has been applied to the reaction involving the replacement of an amino hydrogen atom by an acyl radical, without conventional limitation to. a reaction involving ammonia. The replacement of the amino hydrogen atom of 9.

primary amine or a secondary amine by an acyl radical has been considered as being amidiflcation, rather than the formation of a substituted amide, or the formation of an imide or substi-r tuted imide. Such obvious departure from conventional nomenclature has been for purposes of simplicity and to show the similaritybetween certain reactions.

It is desirable to emphasize 'again,that in the hereto appended claims reference to a polybasic carboxy acid includes not only the acid itself, but also various salts and esters thereof, and also other functional equivalents, such as the anhydrides, acyl chlorides, etc. Furthermore, in the hereto appended claims, reference to the product derived by reaction between an acid ester of the kind previously described and an amine of the kind previouslydescribed, is meant to refer to such products in all its various modifications previously referred to, to' wit, such instances where carboxylic hydrogen atoms appear as such, or have been replaced by metallic atoms, organic radicals derived from various alcohols, amine radicals, or residues, etc.; and as to thepresence of any basic amine nitrogen atom, it may be in the amine form, or in a salt form, or ina base form, as, for example, obtainable by contact with water. The functional equivalents of all these variations have been pointed out previously, and were readily comprehended; and the scope of the claims, in light of such obvious equivalents, requires no further discussion.

In considering the compositions of matter herein disclosed, at least to the extent that they arederivedfrom basic diols, it is necessary to appreciate such substances are not resins in the sense that such term is used to indicate materials which are obtained from the same raw materials combined in different proportions and un der different conditions of reaction. The simplest resin formation may be exemplified by the reaction between ethylene glycol and phthalic acid. The product of such reaction may be indicated by the following formula:

on[cimooccoo] a diol, to wit, ethylene glycol, and would be indicated thus:

If a monoglyceride be denoted, thus:

on acoomm Q and a diglyceride be denoted, in the following manner:

(R.COO) 2C3H5OH it becomes obvious that phthalated derivatives thereof may be indicated thus:

COOH

In a dibasic acid, such as phthalic acid and the like, where the two carboxyl groups are either attached to adjacent carbon atoms or carbon atoms which are relatively close together, and where the distances from the carboxyl radicals to the common carbon atom chain are substantially uniform, resinification takes place readily. In other words, in the product as exemplified by the diol derived by esterifying a mole of triethanolamine with a mole of a fatty acid, the product reacts readily with phthalic anhydride under proper conditionsto produce a resinous material, as previously indicated. Such resinous material B.COO.C:HI

may be modified by introduction of a fatty acid,-

so as to stop further growth by reacting with the available hydronl. Such material as a resin would be comparable to a modified special alkyd resin.

If, however, phthalic anhydride,.as such, is not used in the free state, but instead, is used in a state where one carboxyl has been united with a hydroxylated fatty body, such as a monoglyceride, or a diglyceride, or the like, as previously described, then such materials are apt to be monobasic, and hence, not resin-forming. However, even where they are dibasic, they do not react to produce resins, and do not build up molecules of a resinous nature, in conjunction with basic diols, for various reasons, some of which are apparent, andsome of which are not. In the first place, steric hindrances possibly prevent tandem contact. In the second place, the basicity of the nitrogen atom tends to form inner salts. The space distances between carboxyl radicals becomes large in terms of the intervening atoms or radicals. The alcoholic hydroxyls of the partially esterified glyceryl radical or similar radicals, is characterized by the fact that there is also attached thereto another long chain monobasic carboxy acid radical, which may have an interfering efi'ect to a marked degree. Finally, the molecular reactions really involve three-dimension components, and the final product is of three dimensions. Chemical formulae, as above employed, are at the best limited to two dimensions. It is diificult to contemplate such complex reaction of actual three-dimensional combinations, based on structural formulae of two dimensions only. However, enough has been said in this discussion to enable one to realize that the compounds herein contemplated, particularly when derived from basic diols, should not be confused with resinous materials.

For convenience, in the present instance, the expression diol has been used in reference to the material derived by an esterification of the hydroxyl triethanolamine, or the like. Similarly, the expression trihydric will be conveniently used to indicate combinations that have at least three alcoholic hydroxyl radicals, and thus would include materials which actually have more than three; for instance, materials which have four or more hydroxyl radicals obtained, for instance, by derivatives of dihydroxy stearic acid, or from glycerylamines, or both. Obviously, a polybasic carboxy acid having more than two carboxyl radicals still acts as if itonly had two carboxy radicals in such instances where one of such radicals has been rendered inactive by esterification, or salt formation, as in the instance of'monosodium salt of citric acid, to which previous reference has been made.

The method of using the herein described compound or composition of matter to resolve a pctroleum emulsion of the water-in-oil type is clearly disclosed in my parent application, Serial No. 211,038, filed May 31, 1938, which subsequently matured as U. S. PatentNo. 2,166,433, dated July 18, 1939, of which the present application is a continuation in part.

Having thus described my invention, what I claim .as new and desire to secure by Letters in which OHRCOO represents the oxy-acyl radical derived from a hydroxylated fatty acid; T represents a member of the class consisting of hydrocarbon radicals and the acylated radicals obtained by replacing the hydrogen atom of the hydroxyl group of an alkylol radical by the acyl radical of a monobasic carboxy acid having less than 32 carbon atoms; n represents a small whole number which is less than 10; m represents the numeral 1, 2, or 3; 112. represents the numeral 0, 1 or 2, and 122" represents the numeral 0, 1 or 2, with the proviso that m+m'+m"=3; and (B) an acidic ester derived by reaction .between a polybasic carboxy acid and a hydroxylated ester of a monobasic detergent-forming carboxy acid; said hydroxylated ester containing at least one hydroxyl radical attached to the alcohol residue; and said acidic ester being characterized by the presence of at least one carboxyl radical.

2. The product resulting from an esteriflcation reaction between (A) an amine of the formula type:

(OH.RC 0 O. CnHi) N in which OI-LRCOO represents the oxy-acyl radical derived from a hydroxylated fatty acid; T represents a member of the class consisting of hydrocarbon radicals and the acylated radicals obtained by replacing the hydrogen atom of the hydroxyl group of an alkylol radical by the acyl radical of a monobasic carboxy acid having less than 32 carbon atoms; 11. represents a small whole number which is less than 10; m represents the numeral 1, 2, or 3; m represents the numeral 0, 1 or 2, and m" represents the numeral 0, 1 or 2, with the proviso that m+m'+m=3; and (B) an acidic ester derived by reaction between a dibasic carboxy acid and a hydroxylated ester of a monobasic detergent-forming carboxy acid; said hydroxylated ester containing at least one hydroxyl radical attached to the alcohol residue; and said acidic ester being characterized by the presence of at least one carboxyl radical.

3. The product resulting from an esterincation reaction between (A) an amine of the formula ype:

(El-u in which OHRCOO repments the oxy-acyl radical derived from a hydroxylated fatty acid; T represents a member of the class consisting of hydrocarbon radicals and the acylated radicals obtained by replacing ahydrozen atom of the hydroml group of an alkylol radical by the acyl radical of a monobasic carboxy acid having less than 32 carbon atoms; Cam being an aliphatic radical; n represents a small whole number which is less than 10; m represents the numeral 1, 2 or 3; m represents the numeral 0, 1 or 2, and 121." represents the numeral 0, 1 or 2, with the proviso that m-l-m'+m"=3; and (B) an acidic ester derived by reaction between a diabasic carboxy acid and a hydroiwlated ester of a monobasic detergent-form ng carboxy acid; said hydroxylated ester containing at least one hydroxyl radical attached to the alcohol residue; and said acidic ester being characterized by the presence of at least one carbonl radical.

i. The product resulting from an esterification reaction between (A) an amine of the formula yp connooocinom mm" in which OHRCOO represents the oxy-acyl radical derived from a hydroxyiated fatty acid; T

represents a member of; the class consisting of hydrocarbon radicals and the acylated radicals obtained by replacing a hydrogen atom of the hydrowl group of an allnvlol radical by the acyl radical of a monobasic carboxy acid having less than 32 carbon atoms; m represents the numeral 1, 2 or 8; m represents the numeral 0, 1 or 2, and m" represents the numeral 0, 1 or 2, with the proviso that m+m'+m"=3; and (B) an acidic ester derived by reaction between a dibasic carboxy acid and a hydroxylated ester of a fatty acid; said hydroxylated ester containing at least one hydroxyl radical attached to the alcohol residue; and said acidic ester being characterized by the presence of at least one carbozwl radical.

5. The product resulting from an esterification reaction between (A) an amine of the formula p in which OHRCOO represents the oxy-acyl radical derived from a hydroxylated fatty acid; T represents a hydrocarbon radical; m represents the numeral 1, 2 or 3; m represents the numeral 0, 1 or 2, and m" represents the numeral 0, 1 or 2, with the proviso that m+m'+m"=3; and (B) an acidic ester derived by reaction between a dibasic carboxy acid and the numeral 0, 1 or 2, with the proviso that-- 1n+m'=3; and (B) an acidic ester derived by reaction between a dibasic carbon acid and a hydroxylated ester of a fatty acid; said hydroxylated ester containing at least one hydroxyl rad ical attached to the alcohol residue; and said acidic ester being characterized by the presence of at least one carbowl radical.

'7 The product resulting from an esteriiication reaction between (A) an amine of the formula type:

(OHLRCOQCzHO mN(H) w ical derived from ricinoleic acid; m represents the numeral 1, 2 or 3,'m' represents the numeral 0, l or 2, with the proviso that m+m'=3.; and (B) an acidic ester derived by reaction between i a dibasic carboxy acid and a hydroiwlated ester of a fatty acid; said hydroxylated ester containing at least one hydroxyl radical attached to the alcohol residue; and said acidic ester being characterized by the presence 01' at least one carbon! radical. 4

8. 'flie product resulting from an esteriiication treaction between (A) an amine oi the formula ype:

(OHRCOO.C2H4) 1.N(I:I) w

in which OHRCOO represents the oxy-acyl radical derived from ricinoleic acid; m represents the numeral 1,. 2 or 3; 111. represents the numeral 0, 1 or 2, with the proviso that m+m'=3; and (B) an acidic ester derived by reaction between a dibasic carboxy acid and a hydroxylated ester of ricinoleic acid; said hydroxylated ester containing at least one hydroxyl radical attached to the alcohol residue; and said acidic ester being characterized by the presence of at least one carboxyl radical.

9. The product resulting from an esteriflcation reaction between (A) an amine of the formula ype:

(0H.RCOO.C2H4) mN (H) m in which OHBCOO represents the oxy-acyl radical derived from ricinoleic acid; m represents the numeral 1, 2 or 3; m represents the nu meral 0, 1 or 2, with the proviso that m+m=3; and (B) an acidic ester derived by reaction between phthalic anhydride and a hydrowlated he in which OHRCOO represents the ow-acyl rad-- ester of ricinoleic acid; said hydroxylated ester containing at least one hydroxyl radical attached to the alcohol residue; and said acidic ester being characterized by the presence of at least one carboxyl radical.

DE GROO'I'E.

CERTIFICATE OF CORRECTI ON.

Patent No. 2,.19h,6h5. March 26,v 191;"0. MELVIN DE GROOTE.

It is hereby certified that error appears -in the printed specification of the above numbered patent requiring correction as follows: Page 2, first oolumn, line 1414., At the end of the line of formula, for (OH)" rea'd --(OH) and that the said Letters Patent should be read with this correction therein that the same may conform to the recordof the case the Patent Office.

Signed and sealed this 50thday of July, A. 1-D. 1911b.

Henry Arsdsle (Seal) v I Acting Commissioner of Patents. 

